Methods for printing on glass

ABSTRACT

A method for printing ink on a substrate comprising the steps of coating a glass substrate with an adhesion promoter, depositing one or more layers of ink on the coated substrate, and laminating the imaged substrate. The substrate can be a glass substrate, and the adhesion promoter can include a silane material, powder coating, organophosphate primer suspended in isopropanol.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority under 35 U.S.C. §119 ofU.S. Provisional Application Ser. No. 61/939,439, filed on Feb. 13,2014, the content of which is relied upon and incorporated herein byreference in its entirety.

BACKGROUND

The use of ink jet printing processes in the manufacture of multicolorimages is known in the art. In such processes, ink droplets can beemitted from a nozzle and deposited on substrates to form an image. Toobtain quality images, rapid absorption of the ink into the substrate isrequired, but at the same time the ink colorant must be retained at ornear the surface of the substrate with lateral ink migration limited tothe resolution of the printer.

To achieve high quality images in ink jet printing, the substrate can becoated with a formulation to meet certain requirements. Although paperstock is extensively used as a substrate for ink jet printing, manyother materials can be used including plastic films and sheets, fabrics,metals, wood, glass, and the like. When transparencies are to beproduced, typically a coated transparent plastic film or sheet is usedas the substrate. Since aqueous based inks are a common type of ink usedin ink jet printing processes, substrate coating formulations typicallyare hydrophilic and contain appropriate absorptive materials. Suchcoated substrates are described in U.S. Pat. No. 4,775,594 and U.S. Pat.No. 5,198,306. The '594 patent describes an ink jet transparency withwetting properties resulting in even surface distribution of ink on thetransparency. The transparency comprises a transparent resinous supportand a clear coating thereon containing a water soluble resin, a waterinsoluble resin, a fluorosurfactant, and non-volatile organic acidincluding glycolic, methoxy acetic, dibasic carboxylic, or tribasiccarboxylic acid. The '306 patent describes a recording transparency andits method of preparation from a water solution. The transparencycomprises a transparent substrate and a coating of a synthetictransparent cellulosic polymer and a surfactant composition comprisingnonionic detergent, anionic detergent and complexing agent.

Conventional ink jet printing processes, inks and substrates are capableof producing high quality four color images on paper substrates in sizesranging from office copy up to sizes useful for posters, displays andbillboards. However, application of ink jet printing has been limitedlargely to typical office uses such as copy and the like whereenvironmental and abrasion damage to the finished ink image is unlikelyto occur. When used as posters, displays, billboards and when used withglass substrates, water sensitive ink jet images and underlyingsubstrates must be protected from rain, sunlight (UV), and otherenvironmental contaminants and should likewise be protected fromabrasion and graffiti to provide adequate useful life to the imagedisplayed. There also continues to be an industry need for a process toprovide protected, durable, distortion-free, scratch-resistant, UV andhumidity resistant, full-color ink jet images for use on large formatposters, billboards, planar surfaces, architectural surfaces,appliances, non-planar surfaces, and the like.

SUMMARY

Some embodiments of the present disclosure include a method for printingink on a glass substrate. The method includes coating a glass substratewith a silane material, depositing a first layer of ink on the coatedglass substrate, depositing a second layer of ink over the first layerof ink, and depositing a powder coating onto the second layer of ink.

Other embodiments include a method for printing ink on a glass substratehaving the steps of depositing a first powder coating on a glasssubstrate, depositing a first layer of ink on the coated glasssubstrate, depositing a second layer of ink over the first layer of ink,and depositing a second powder coating onto the second layer of ink.

Additional embodiments include a method for printing ink on a substratecomprising the steps of coating a glass substrate with an adhesionpromoter, depositing a first layer of ink on the coated substrate,depositing a second layer of ink over the first layer of ink, anddepositing a powder coating onto the second layer of ink.

Another embodiment includes a method for printing ink on a substratecomprising the steps of pretreating a glass substrate, depositing one ormore layers of ink on the pretreated glass substrate, overprinting thedeposited one or more layers of ink with an overcoat, and curing theoverprinted glass substrate to encapsulate the deposited one or morelayers of ink.

Additional embodiments include a method for printing ink on a substratecomprising the steps of pretreating a substrate with an organophosphateprimer suspended in an isopropanol solution, depositing one or morelayers of ink on a first surface of the pretreated substrate, andlaminating a film onto to the first surface to form an imaged laminate.

Yet another embodiment includes a laminate comprising a substratepretreated with an organophosphate primer suspended in an isopropanolsolution, one or more layers of ink deposited on a first surface of thepretreated substrate, and a film laminated on the one or more layers toform an imaged laminate.

Additional features and advantages of the claimed subject matter will beset forth in the detailed description which follows, and in part will bereadily apparent to those skilled in the art from that description orrecognized by practicing the claimed subject matter as described herein,including the detailed description which follows, the claims, as well asthe appended drawings.

It is to be understood that both the foregoing general description andthe following detailed description present embodiments of the presentdisclosure, and are intended to provide an overview or framework forunderstanding the nature and character of the claimed subject matter.The accompanying drawings are included to provide a furtherunderstanding of the present disclosure, and are incorporated into andconstitute a part of this specification. The drawings illustrate variousembodiments and together with the description serve to explain theprinciples and operations of the claimed subject matter.

BRIEF DESCRIPTION OF THE DRAWINGS

For the purposes of illustration, there are forms shown in the drawingsthat are presently preferred, it being understood, however, that theembodiments disclosed and discussed herein are not limited to theprecise arrangements and instrumentalities shown.

FIG. 1 is a diagram of an exemplary procedure for one embodiment of thepresent disclosure.

FIG. 2 is a diagram of an exemplary procedure for another embodiment ofthe present disclosure.

FIG. 3 is a diagram of an exemplary procedure for a further embodimentof the present disclosure.

FIG. 4 is a diagram of an exemplary procedure for an additionalembodiment of the present disclosure.

FIGS. 5A-5N are plots of exemplary embodiments measured for color shiftwith a spectrometer after certain experiments.

FIG. 6 is a diagram of another procedure for an embodiment of thepresent disclosure.

FIG. 7 is a simplified illustration of one embodiment of the presentdisclosure.

FIG. 8 is a series of interval plot of mean color shifts for someembodiments.

FIG. 9 is a plot of pummel rating for some embodiments.

FIG. 10 is an interval plot of pummel values for some embodiments.

FIG. 11 is an individual value plot showing the individual measurementsfor some embodiments.

DETAILED DESCRIPTION

In the following description, like reference characters designate likeor corresponding parts throughout the several views shown in thefigures. It is also understood that, unless otherwise specified, termssuch as “top,” “bottom,” “outward,” “inward,” and the like are words ofconvenience and are not to be construed as limiting terms. In addition,whenever a group is described as comprising at least one of a group ofelements and combinations thereof, it is understood that the group maycomprise, consist essentially of, or consist of any number of thoseelements recited, either individually or in combination with each other.

Similarly, whenever a group is described as consisting of at least oneof a group of elements or combinations thereof, it is understood thatthe group may consist of any number of those elements recited, eitherindividually or in combination with each other. Unless otherwisespecified, a range of values, when recited, includes both the upper andlower limits of the range. As used herein, the indefinite articles “a,”and “an,” and the corresponding definite article “the” mean “at leastone” or “one or more,” unless otherwise specified.

The following description of the present disclosure is provided as anenabling teaching thereof and its best, currently-known embodiment.Those skilled in the art will recognize that many changes can be made tothe embodiment described herein while still obtaining the beneficialresults of the present disclosure. It will also be apparent that some ofthe desired benefits of the present disclosure can be obtained byselecting some of the features of the present disclosure withoututilizing other features. Accordingly, those who work in the art willrecognize that many modifications and adaptations of the presentdisclosure are possible and may even be desirable in certaincircumstances and are part of the present disclosure. Thus, thefollowing description is provided as illustrative of the principles ofthe present disclosure and not in limitation thereof.

Those skilled in the art will appreciate that many modifications to theexemplary embodiments described herein are possible without departingfrom the spirit and scope of the present disclosure. Thus, thedescription is not intended and should not be construed to be limited tothe examples given but should be granted the full breadth of protectionafforded by the appended claims and equivalents thereto. In addition, itis possible to use some of the features of the present disclosurewithout the corresponding use of other features. Accordingly, thefollowing description of exemplary or illustrative embodiments isprovided for the purpose of illustrating the principles of the presentdisclosure and not in limitation thereof and may include modificationthereto and permutations thereof.

Ink jet technology is not conventionally employed for production ofprinting techniques on non-porous media, e.g., glass or othersubstrates, due to low adhesion characteristics on these substrates.Pretreatment of glass substrates has been employed in the industry;however, such methods have heretofore been unsuccessful in achievinghigh-quality prints. For example, pretreatment sprays such as, but notlimited to, silane or other primers, have been utilized by the industryto increase the adhesion characteristics of ink to glass substrates tothe level of other printing technologies (e.g., screen printing, padprinting) but this alone does not provide high quality adhesioncharacteristics. While some embodiments reference ink jet printing onglass substrates, the claims appended herewith should not be so limitedas embodiments are applicable to other methods of printing such as, butnot limited to, direct-to-substrate printing, dye sublimation, padprinting, etc. as well as other media, e.g., plastics, ceramics, etc.

Some embodiments of the present disclosure, however, can utilizeconventional silane, or other, pretreatment methods and can incorporatea powder coating protective layer to encapsulate the decorative ink jetlayer. This can therefore protect the printed substrate from theenvironment or other external events (e.g., scratching, etc.). Inadditional embodiments, the powder coating layer can be used as a colorbacker to broaden the ink jet color gamut (i.e., powder coating comes ina metallic silver, ink jet does not).

FIG. 1 is a diagram of an exemplary procedure for one embodiment of thepresent disclosure. With reference to FIG. 1, a procedure 100 isillustrated for providing a high quality printed image on a glasssubstrate. In step 110, an exemplary substrate such as, but not limitedto, a glass substrate can be pre-treated with an adhesion promoter. Anexemplary adhesion promoter utilized by some embodiments can be silaneto increase ink adhesion to the substrate. In some embodiments, step 110can include cleaning the substrate, pyrolysis of the substrate and thenspraying of a silane treatment on the substrate. Of course, othermethods of providing a silane treatment onto a substrate are envisionedand such an example should not limit the scope of the claims appendedherewith. For example, a silane treatment can be provided on a substrateby dipping, vapor deposition, painting, printing, etc. Exemplary silanescan include silanes having no functional groups or one or morefunctional groups. Some functional silanes or silanols can be utilizedto assist in the adhesion of inks to the underlying substrate.Non-limiting compounds having 2 reactive silyl groups include hydroxyterminated polydimethylsiloxanes and polydiethylsiloxanes (i.e., havingSi—OH terminal groups). Other compounds can include three or morereactive silyl groups per molecule, e.g., alkoxy silyl or acyloxy silylgroups, 1,3-dimethyltetramethoxydisiloxane,methacryloxypropyl-trimethoxysilane, tetraethoxy-silane,1,3-dioctyltetramethoxy-disiloxane, glycidoxypropyltrimethoxysilane,3-bromopropyltrimethoxysilane, and dioctyltetraethoxydisiloxane, to namea few. In step 120, a first ink layer can be deposited or provided overthe coated substrate. This first ink layer can be deposited usingconventional ink jet technology and can include any various artwork,customized or otherwise. Step 120 can include depositing one or more inkimages on the substrate. For example, an ink jet device can traverseover the substrate and deposit ink droplets on the coated substrate toform an imaged layer. An exemplary ink jet device can be anyconventional ink jet printer used to print a single color or a fullcolor image. Conventional ink jet printing methods and devices aredisclosed by Werner E. Haas in “Imaging Processes and Materials,” Ed. bySturge, Walworth & Shepp, which is incorporated herein in its entiretyby reference thereto. Additional ink jet devices include, but are notlimited to, Hewlett Packard Desk Jet 500 and 500C printers, IBM Lexmark®ink jet printers, Cannon Bubblejet® printers, NCAD Computer CorporationNovajet® printers, and the like. In this step, a single color ink image,e.g., black, green, etc., can be deposited or several colors can bedeposited either in sequence or simultaneously, to form an ink imagedlayer, e.g., a four color subtractive color image including yellow,magenta, cyan and black images in register. Unless the printed ink layeris to be used in the manufacture of a transparency, the ink imagetypically is printed on the substrate as a reverse or mirror image sothat the completed protected ink image will possess correct orientationwhen applied to an opaque substrate. Exemplary inks used in embodimentsinclude ink compositions such as, but not limited to, liquidcompositions comprising a solvent or carrier liquid, dyes or pigments,humectant, organic solvents, detergents, thickeners, preservatives, andthe like. The solvent or carrier liquid can typically be water, althoughink in which organic materials such as polyhydric alcohols as thepredominant solvent or carrier can also be used. The dyes used in suchcompositions are typically water-soluble direct or acid type dyes.

In step 130, a second ink layer can be deposited onto the first inklayer also using ink jet technology described above. Of course, thissecond ink layer can utilize the same or different technology than whatwas used to deposit the first layer. In some embodiments, the second inklayer can be solid white (or another suitable color(s)) to reduce oreliminate the transparency of the underlying glass substrate and providea clearer picture of the image deposited in the first layer to anobserver. In step 140, a powder coating can be deposited onto the secondink layer to provide a scratch- and environmentally-resistant coatingfor the ink layers. Exemplary powder material can include inorganicparticles such as silicas, chalk, calcium carbonate, magnesiumcarbonate, kaolin, calcined clay, pyrophylite, bentonite, zeolite, talc,synthetic aluminum and calcium silicates, diatomatious earth, anhydroussilicic acid powder, aluminum hydroxide, barite, barium sulfate, gypsum,calcium sulfate, and the like. Suitable powder material can also includeorganic particles such as polymeric beads including beads ofpolymethylmethacrylate, copoly(methylmethacrylate/divinylbenzene),polystyrene, copoly (vinyltoluene/t-butylstyrene/methacrylic acid),polyethylene, and the like. The composition and particle size of theparticles can be selected so as not to impair the transparent nature ofthe deposited ink. The powder material can be substantially transparentor can include a colorant. In some embodiments, the powder material caninclude components which strongly absorb ultraviolet radiation therebyreducing damage to underlying images by ambient ultraviolet light, e.g.,such as 2-hydroxybenzophenones; oxalanilides, aryl esters and the like,hindered amine light stabilizers, such asbis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and the like, andcombinations thereof. Other suitable powder coatings can includethermally activated, hydrophilic, adhesive material comprised ofthermoplastic polyurethanes, polycaprolactone, acrylic copolymers, andcombinations thereof. In some embodiments, the coated substrate can thenbe heat-treated or cured.

FIG. 2 is a diagram of an exemplary procedure for another embodiment ofthe present disclosure. With reference to FIG. 2, a procedure 200 isillustrated for providing a high quality printed image on a glasssubstrate. In step 210, an exemplary substrate such as, but not limitedto, a glass substrate can be pre-treated with an adhesion promoter. Anexemplary adhesion promoter utilized by some embodiments can be a powdercoating which is sprayed directly on the glass to increase ink adhesionto the substrate. Other adhesion promoters can include3-glycidoxypropyltrimethoxysilane (DOW Z-6040 from Dow Corning),tris[3-(trimethoxysilyl)propyl]-isocyanurate (Geniosil GF 69 fromWacker), aminopropyl triethoxy silane, bis(trimethoxysilylpropyl)amine,or combinations thereof. In some embodiments, step 210 can also includecuring or heating of the powder coating on the substrate. Exemplarypowder material can include inorganic particles such as silicas, chalk,calcium carbonate, magnesium carbonate, kaolin, calcined clay,pyrophylite, bentonite, zeolite, talc, synthetic aluminum and calciumsilicates, diatomatious earth, anhydrous silicic acid powder, aluminumhydroxide, barite, barium sulfate, gypsum, calcium sulfate, and thelike. Suitable powder material can also include organic particles suchas polymeric beads including beads of polymethylmethacrylate,copoly(methylmethacrylate/divinylbenzene), polystyrene, copoly(vinyltoluene/t-butylstyrene/methacrylic acid), polyethylene, and thelike. The composition and particle size of the particles can be selectedso as not to impair the transparent nature of the ink to be deposited.The powder material can be substantially transparent or can include acolorant. In some embodiments, the powder material can includecomponents which strongly absorb ultraviolet radiation thereby reducingdamage to underlying images by ambient ultraviolet light, e.g., such as2-hydroxybenzophenones; oxalanilides, aryl esters and the like, hinderedamine light stabilizers, such as bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate and the like, and combinations thereof. This first powdercoating can be utilized to permanently adhere printed ink to theunderlying substrate. Other suitable powder coatings can includethermally activated, hydrophilic, adhesive material comprised ofthermoplastic polyurethanes, polycaprolactone, acrylic copolymers, andcombinations thereof.

In step 220, a first ink layer can be deposited or provided over thecoated substrate. This first ink layer can be deposited usingconventional ink jet technology and can include any various artwork,customized or otherwise. Step 220 can include depositing one or more inkimages on the substrate. For example, an ink jet device can traverseover the substrate and deposit ink droplets on the coated substrate toform an imaged layer. An exemplary ink jet device can be anyconventional ink jet printer used to print a single color or a fullcolor image. Conventional ink jet printing methods and devices aredisclosed by Werner E. Haas in “Imaging Processes and Materials,” Ed. bySturge, Walworth & Shepp, which is incorporated herein in its entiretyby reference thereto. Additional ink jet devices include, but are notlimited to, Hewlett Packard Desk Jet 500 and 500C printers, IBM Lexmark®ink jet printers, Cannon Bubblejet® printers, NCAD Computer CorporationNovajet® printers, and the like. In this step, a single color ink image,e.g., black, green, etc., can be deposited or several colors can bedeposited either in sequence or simultaneously, to form an ink imagedlayer, e.g., a four color subtractive color image including yellow,magenta, cyan and black images in register. Unless the printed ink layeris to be used in the manufacture of a transparency, the ink imagetypically is printed on the substrate as a reverse or mirror image sothat the completed protected ink image will possess correct orientationwhen applied to an opaque substrate. Exemplary inks used in embodimentsinclude ink compositions such as, but not limited to, liquidcompositions comprising a solvent or carrier liquid, dyes or pigments,humectant, organic solvents, detergents, thickeners, preservatives, andthe like. The solvent or carrier liquid can typically be water, althoughink in which organic materials such as polyhydric alcohols as thepredominant solvent or carrier can also be used. The dyes used in suchcompositions are typically water-soluble direct or acid type dyes. Instep 230, a second ink layer can be deposited onto the first ink layeralso using ink jet technology described above. Of course, this secondink layer can utilize the same or different technology than what wasused to deposit the first layer. In some embodiments, the second inklayer can be solid white (or another suitable color(s)) to reduce oreliminate the transparency of the underlying glass substrate and providea clearer picture of the image, deposited in the first layer, to anobserver. In step 240, a second powder coating can be deposited onto thesecond ink layer to provide a scratch- and environmentally-resistantcoating for the ink layers. The material utilized in the second powdercoating can be the same or different than the first powder coating asdescribed above. The second powder coating can be substantiallytransparent or can include a colorant. In some embodiments, the coatedsubstrate can then be heat-treated or cured.

FIG. 3 is a diagram of an exemplary procedure for a further embodimentof the present disclosure. With reference to FIG. 3, a procedure 300 isillustrated for providing a high quality printed image on a glasssubstrate. In step 310, an exemplary substrate such as, but not limitedto, a glass substrate can be pre-treated with an adhesion promoter.Exemplary adhesion promoters include, but are not limited to, silanesand powder coatings, each of which are described above with reference toFIGS. 1 and 2, respectively. As glass is a non-porous substrate with arelatively inert surface, UV inks do not generally adhere to glasswithout an adhesion promoter. For example, using an ASTM standardcross-hatch test, tape can easily remove ink from the glass once pulledif no adhesion promoter is employed. Silane-based adhesion promoter canbe applied to the glass substrate. In some embodiments, the substratecan be wiped with a conventional solvent, torch treated and then sprayedwith an exemplary silane primer. In step 320, a first ink layer can bedeposited or provided over the coated substrate. This first ink layercan be deposited using conventional ink jet technology and can includeany various artwork, customized or otherwise. In step 330, a second inklayer can be deposited onto the first ink layer also using ink jettechnology. This second ink layer can utilize the same or differenttechnology than what was used to deposit the first layer. In someembodiments, the second ink layer can be solid white (or anothersuitable color(s)) to reduce or eliminate the transparency of theunderlying glass substrate and provide a clearer picture of the imagedeposited in the first layer to an observer. In step 340, a powdercoating can be deposited onto the second ink layer to provide a scratch-and environmentally-resistant coating for the ink layers. This powdercoating can be substantially transparent or can include a colorant. Insome embodiments, the coated substrate can then be heated or cured.

While substrates heretofore have been generically referred to assubstrates or glass substrates, the claims appended herewith areapplicable to any type of substrate, glass or otherwise (metal,transparent film, etc.). In some embodiments having a glass substrate,the glass can be chemically-strengthened or non-chemically-strengthenedglass. For those chemically strengthened embodiments, an ion exchangeprocess can be utilized which can comprise exchanging Na, Li or Na andLi ions in the surface of the glass for large alkali ions. Theion-exchange can occur to a depth of approximately 40 μm from thesurface of the glass substrate. Of course, the depth of ion-exchange canbe greater or less than 40 μm. For example, some embodiments can includechemically strengthened glass (e.g., Gorilla Glass) having a highcompressive stress (CS) level, a relatively high depth of compressivelayer (DOL), and/or moderate central tension (CT). The thicknesses ofthis glass can range from 0.3 mm to 2.1 mm or greater. Other embodimentscan include thinner chemically strengthened or non-chemicallystrengthened glass such as Willow Glass. Such thicknesses can be lessthan 0.5 mm to 0.1 mm or thinner. It is also contemplated that the glasssubstrate can be a soda lime glass, an alkali containing aluminosilicateglass, an alkali containing aluminoborosilicate glass, an alkalicontaining borosilicate glass, an alkali containing glass-ceramic orother glass known by those skilled in the art.

Utilizing embodiments described herein, an exemplary powder coating canprevent damage to the ink layer and therefore create an industryaccepted ink jet on glass product. By printing on the backside of theglass and encapsulating the ink jet layer with a hardened powder coatinglayer, the problem of durability can be solved. Further, in someembodiments, by spraying a layer of powder coating directly on theglass, printing on the powder coating, and then encapsulating withanother layer of powder coating the adhesion problem can be solved.

Exemplary embodiments provide cost effective powder coatings that arerecyclable and emit zero or near zero volatile organic compounds.Embodiments can also provide high temperature resistance, high fracturetoughness, cracking resistance, and protection of underlying ink jetlayers. Exemplary embodiments can also utilize a transparent powdercoating layer or a color powder coating layer to encapsulate the imageand also to broaden the ink jet color gamut. Through such processes,exemplary embodiments can utilize antimicrobial additives to one or moresurfaces of the glass substrate and can provide color stability andhermetic sealing of images not provided by conventional processes.Exemplary processes described above can meet chemical testing andhardness and scratch testing after water bath, cyclic moisture, dryheat, NaOH, H₂SO₄, and mineral oil exposures. Further, exemplaryprocesses described above can meet mechanical testing such as a 5Brating on cross-hatch adhesion tests and above a 3H rating on pencilhardness tests. Embodiments herein also provide a broader range ofthermal stability, the ability for use of ink jetted glass substrates inexternal environments, use of ink jetted glass substrates in lightingand informational applications. Due to the various uses of chemicallystrengthened glass as a glass substrate, additional applications includeanti-counterfeiting codes, anti-graffiti applications, printing ofunique codes on curved glass, customized artwork on curved substrates(e.g., appliances) and customized decorated glass for automotiveapplications.

According to some embodiments, photographic images or art workreproductions can be printed and made into “framed pictures” to bedisplayed as wall décor or on a desk or some other surface in the homeor office environment. Other methods of displaying such picturesaccording to embodiments herein can use non-framed media such as canvas,metal, wood, acrylic or glass. An alternative to direct printing can beto mount a conventionally processed (e.g., wet processed) photograph ona substrate which takes advantage of the highly mature photo printingmethods and adds a modern look to the final product. Some embodimentscan employ dye sublimation which utilizes specialty inks and aconventional inkjet printer. Exemplary inks can contain dyes thatsublimate at high temperature, typically around 200° C. In such anexemplary method, one can first print an image onto a transfer mediawhereby the image can be placed on the final substrate that is to becoated with a dye-receiving material. This stack can then be heated toapproximately 200° C. under constant pressure whereby dye moleculesleave the transfer media and form a color image on the substrate. In adye sublimation process, the image quality can be photographic andindistinguishable from a real photograph when first made. In someembodiments, a top coat with an exemplary UV absorbing material can beused to prolong the transferred image life.

In other embodiments, UV inkjet printing can be utilized to producequality images with exemplary UV endurance. Some inks can bepigment-based and dispersed in a UV-curable clear liquid. For example,in some embodiments the pigment can be carbon black, iron pigment,cobalt pigment, black spinel, cadmium pigment, chromium pigment,titanium pigment, zinc pigment, lead pigment, magnesium pigment,vanadium pigment, copper chromite black spinel, or combinations thereof.Other pigments known to those in the art can also be used. Curing ofsuch inks can be performed by a UV lamp in the vicinity of or adjacentthe inkjet printer. Instant curing of ink droplets can enable printingon a wide range of substrate media including many non-porous types suchas ceramic and glass.

FIG. 4 is a diagram of an exemplary procedure for an additionalembodiment of the present disclosure. With reference to FIG. 4, aprocedure 400 is illustrated for providing a high quality printed imageon a substrate. In step 410, an exemplary substrate such as, but notlimited to, a glass substrate can be prepared by cleaning the substrateof contaminates (organic and inorganic). In some embodiments, this canbe accomplished using typical glass cleaning methods (alcohol,Windex-type cleaners, etc.). In another embodiment, step 410 can includepretreating the substrate with an adhesion promoter. Depending upon theink formulation used, an adhesion promoter may be required whichincludes, but is not limited to, silanes, powder coatings, or otheradhesion promoters each of which are described above with reference toFIGS. 1, 2 and 3. In step 420, one or more ink layers can be depositedor provided over the cleaned and/or coated substrate. These ink layerscan be deposited using conventional ink jet technology or othertechnology described above and can include any various artwork,customized or otherwise. In some embodiments, the layer(s) can be opaqueor can be semi-transparent to take advantage of the color of anencapsulation layer to be added in a further step. In step 430, thedeposited ink layers can be overprinted with a screen print forencapsulation purposes. For example, using a screen print ink color ofchoice (e.g., white, black, or other suitable color), an overcoat of asolid color can be deposited on the ink layers to reduce or eliminatethe transparency of the underlying glass substrate and provide a clearerpicture of the image deposited in the first layer to an observer. Instep 440, the deposited ink layers and overprinted coat can then becured to thereby encapsulate the images formed by the ink layers and/orcoat. In some embodiments, the step 440 includes curing the ink using aUV lamp, a heat lamp, etc. In another embodiment, a powder coating canbe deposited onto the ink layers to provide a scratch andenvironmentally-resistant coating therefor. This coated substrate canalso be heated or cured.

FIGS. 5A-5N are plots of exemplary embodiments measured for color shiftwith a spectrometer after certain tests. With reference to FIGS. 5A-5N,measurements of individual colors (e.g., cyan/blue, magenta/red, yellow,black, light cyan/turquoise, light magenta/pink, white) and a lightmarble design for color fade/shift were conducted in three differentenvironmental testing experiments (e.g., damp heat, high temperature andthermal cycling testing). During these experiments, all colors wereinkjet printed followed by a screen print. The light marble design wasprinted as a semi-transparent inkjet followed by a screen print. Eachmeasurement illustrated in FIGS. 5A-5N were taken using common LAB colorreading on a spectrophotometer where L represents the lightness, orposition between black (0) and white (100), A represents color positionbetween green (value −) and magenta (value +), and B represents colorposition between blue (value −) and yellow (value +). As illustrated inFIG. 5A, confidence intervals of mean for lightness (L) of three marblesamples are shown at a time of 0 and 168 hours of damp heat exposure.FIG. 5B provides an illustration of confidence intervals of mean forlightness (L) of four multiple color samples at a time of 0 and 168hours for high temperature exposure. FIG. 5C provides an illustration ofconfidence intervals of mean for lightness (L) of three multiple colorsamples at a time of 0 and 19 hours for thermal cycling exposure. FIG.5D provides an illustration of confidence intervals of mean for positionbetween magenta/green (A) of four multiple color samples at a time of 0and 168 hours for high temperature exposure. FIG. 5E provides anillustration of confidence intervals of mean for position betweenmagenta/green (A) of three multiple color samples at a time of 0 and 19hours for thermal cycling exposure. FIG. 5F provides an illustration ofconfidence intervals of mean for position between blue/yellow (B) ofthree marble samples at a time of 0 and 168 hours for damp heatexposure. FIG. 5G provides an illustration of confidence intervals ofmean for position between blue/yellow (B) of four multiple color samplesat a time of 0 and 168 hours for high temperature exposure. FIG. 5Hprovides an illustration of confidence intervals of mean for positionbetween blue/yellow (B) of three multiple color samples at a time of 0and 19 hours for thermal cycling exposure. FIG. 51 provides anillustration of individual values of lightness measurements (L) of threemarble samples at a time of 0 and 168 hours for damp heat exposure. FIG.5J provides an illustration of individual values of measurements forposition between magenta/green (A) of four multiple color samples at atime of 0 and 168 hours for high temperature exposure. FIG. 5K providesan illustration of individual values of measurements for positionbetween magenta/green (A) of three multiple color samples at a time of 0and 19 hours for thermal cycling exposure. FIG. 5L provides anillustration of individual values of measurements for position betweenblue/yellow (B) of three marble samples at a time of 0 and 168 hours fordamp heat exposure. FIG. 5M provides an illustration of individualvalues of measurements for position between blue/yellow (B) of fourmultiple color samples at a time of 0 and 168 hours for high temperatureexposure. FIG. 5N provides an illustration of individual values ofmeasurements for position between blue/yellow (B) of three multiplecolor samples at a time of 0 and 19 hours for thermal cycling exposure.As shown in each of these figures, embodiments of the present disclosureprovide superior adhesion and encapsulated image performance.

FIG. 6 is a diagram of another procedure for an embodiment of thepresent disclosure. With reference to FIG. 6, a procedure 600 isillustrated for providing a high quality printed image on a substrate.In step 610, an exemplary substrate such as, but not limited to, a glasssubstrate can be pre-treated with an adhesion promoter. Exemplaryadhesion promoters include, but are not limited to, silanes, powdercoatings, and other promoters each of which is described above withreference to FIGS. 1, 2 and 3. In an exemplary embodiment, an organicphosphate primer material can be utilized as an adhesion promoter. Insuch an embodiment, the organic phosphate or organophosphate primermaterial can be suspended in a solvent. An exemplary, non-limitingsolvent can be an isopropanol solution. Exemplary organic phosphateprimer materials include, but are not limited to, methacrylatedphosphoric acids, monoalkyl phosphates, dialkyl phosphates,di-n-butylphosphate, and the like. Other examples of suitable phosphatematerials include, but not limited to, vinyl phosphonic acid, vinylphosphonic acid methyl ester, phosphates of hydroxy alkyl acrylates ormethacrylates like the phosphate of 2-hydroxyethyl acrylate, or thephosphate of 2-hydroxyethyl methacrylate, 10-methacryloyloxydecyldihydrogen phosphate, 10-acryloyloxydecyl dihydrogen phosphate,bis(2-acryloyloxyalkyl)acid phosphate, bis(2-methacryloyloxyalkyl)acidphosphate, and the phosphate of caprolactone modified hydroxyalkylacrylate or methacrylate, N-(dimethylphosphonomethyl)acrylamide,phosphonic acid, P-[[(1-oxo-2-propen-1-yl)amino]methyl]-, vinyl-,bis(2-chloroethyl)phosphonic acid ester,tris(2-chloroisopropyl)phosphate, tris(2-chloroethyl)phosphate,tris(1,3-dichloroisopropyl)phosphate, other monomeric and oligomericchloroalkyl phosphate esters, and phosphonic acids, andP-[[bis(2-hydroxyethyl)amino]methyl]-, and diethyl ester, to name a few.In one embodiment, the organic phosphate primer can be Primer Sunflowerprovided by Sun Innovations. The suspended primer or solution can beapplied onto the substrate for a predetermined time (e.g., 10 min, 30min, 1 hour, 2 hours, etc.), a soak, and then washed or wiped with aconventional solvent or water to remove excess material. In anotherembodiment, the glass substrate can be dipped into an exemplary solutionrather than soaked for a predetermined time. After drying the substrate,an exemplary printing process can be employed to print an image on thesubstrate. Experimental testing has resulted in adhesion scores ofgreater than 4B or 5B for one or more weeks in an ASTM cross-hatch test.In some embodiments, the substrate can be planar or can be threedimensional (e.g., curved about one radius, two radii, convex, concave,etc.) to provide additional aesthetics and enhanced functionality. Instep 620, one or more ink layers can be deposited or provided over thepretreated substrate. These ink layers can be deposited usingconventional ink jet technology or other technology described above andcan include any various artwork, customized or otherwise. In someembodiments, the layer(s) can be opaque or can be semi-transparent. Inone non-limiting example, a white ink layer can be applied after one ormore color layers to “pop” the color, similar to what a white paperwould provide to the ink image in conventional printing. In anotherembodiment, a white ink layer can be followed by a black ink layer toassist in stopping any object or features from showing through theprinted image. In a further embodiment where only a white ink layer isdeposited (i.e., no black ink layer), backlighting features can beenabled. In certain embodiments where the white ink contains TiO2particles, an exemplary printer can include an agitation mechanism toprevent separation in the white ink pigment.

In step 630, an anti-splinter film can be laminated to the stack. Asimages, products or pictures can experience impact events throughout itslife, an anti-splinter film can be used to ensure shard retention duringsuch breakage events. An exemplary anti-splinter film can also beutilized to provide a white, frosted, opaque, colored, etc. backing toembodiments of the present disclosure. For example, a film can belaminated to the printed glass using a pressure-sensitive-adhesive (PSA)and a roller laminator. A range of non-limiting polymer film materialscan be used to achieve anti-splinter functionality, e.g., vinyl,polypropylene, high density polyethylene (HDPE), polyvinyl chloride(PVC), and the like. In some embodiments, clear or cloudy polyethyleneterephthalate (PET), metallized polyester, lenticular plastic and/orpolymer dispersed liquid crystals (PDLC) and like materials or modulescan be used in various color schemes. In a preferred embodiment, vinylfilms can be utilized in varying shades of white or other colors andwith varying thicknesses to provide an exemplary product.

In step 640, the laminate can be edge protected and strengthened. Forexample, a sol gel, epoxy resin, or other polymeric coating can bedeposited (spray coated, screen printed or coated, dip coated, etc.) onthe laminate to improve drop strength or edge strength thereof. In onenon-limiting embodiment, a UV curable coating can be utilized to improvedrop strength when applied at the edge of a laminate. In one experiment,a decorated Corning Gorilla Glass laminate as described above wassubjected to and passed 300 subsequent Tumble Drop Tests using anexemplary epoxy coating applied to the edges thereof. In someembodiments, step 640 can include curing the coating using a UV lamp, aheat lamp, etc.

In additional embodiments, the method 600 can take advantage of theflexibility provided by an ink jet printer and can include printing theimage with a variety of border types (e.g., clear border, full bleed,colored border, feather-like border, etc.), can provide lettering on oraround the image, can provide a textured or three-dimensional surface,including ADA compliant features (e.g., Braille), can include ananti-glare or anti-reflection coating on the substrate surface tocontrol gloss level, can include a backlight apparatus or device (e.g.,LED based thin lightbox, etc.).

FIG. 7 is a simplified illustration of one embodiment of the presentdisclosure. With reference to FIG. 7, a laminate structure 700 isprovided having a substrate 710 that can be pretreated with anorganophosphate primer 715 suspended in a solvent, e.g., an isopropanolsolution. Exemplary substrates include, but are not limited to,chemically strengthened glass, non-chemically strengthened glass, metal,canvas, wood, and acrylic substrates. In one embodiment, the substrate710 can be a chemically strengthened glass substrate with a thicknessranging from 0.1 mm to 2.2 mm. Exemplary organophosphate primers can bebut are not limited to, a monoalkyl phosphate, dialkyl phosphate, anddi-n-butylphosphate. The structure 700 further includes one or morelayers of ink 720 deposited on the pretreated surface 715 of thesubstrate 710. A film 730 can be laminated on the one or more layers ofink 720 to form an imaged laminate 700. In some embodiments, the film730 can be an anti-splinter film and can be white or colored. In otherembodiments, the film 730 can be vinyl, polypropylene, high densitypolyethylene (HDPE), polyvinyl chloride (PVC), clear or cloudypolyethylene terephthalate (PET), metallized polyester, lenticularplastic and/or polymer dispersed liquid crystals (PDLC). In furtherembodiments, the laminate structure 700 can include a polymeric material740 coating portions or all of the laminate 700 to strengthen the edgesthereof. While the laminate 700 is illustrated as being planar in form,the claims appended herewith should not be so limited as the laminate700 can be three-dimensional and have radii around one, two or moreaxes, can be concave, convex or another complex shape.

Some embodiments described herein can thus encapsulate ink printed byinkjet on Gorilla Glass utilizing a screenprint backer to improvedurability of glass over time as screenprint inks are generically morerobust than inkjet inks To assess this, the decoration methods of inkjeton glass, inkjet on glass with a screenprint over the inkjet layer, andscreenprint on glass were utilized. During the experiment, embodimentswere characterized using a Barbieri Spectrophotometer in the CIE L*A*Bcolor space. The embodiments were then exposed to different extremeconditions in environmental chambers for 21 days, e.g., high heat at 93°C., ambient humidity damp heat at 60° C., and 95-100% relative humiditythermal cycling from −20° C. to 80° C. and four hour soaks at theseextremes. Color degradation was than evaluated by re-measuring the sameembodiments using the same Barbieri system. In addition to ΔL, ΔA, andΔB, ΔE was calculated which equates to the square root of the sum of thesquares of ΔL, ΔA, and ΔB (see Table 1). As measured and illustrated inFIG. 8, mean color shift was more than 2× for all parameters associatedwith inkjet printing alone as compared with inkjet printing encapsulatedby screenprint. These differences are statistically significant asindicated by the interval plots illustrated in FIG. 8 shown below for ΔBand ΔE.

TABLE 1 Variable Print Method N Mean StDev Delta L IJ 14 1.101 1.186IJ + SP 14 0.4599 0.3237 Delta a IJ 14 1.669 2.351 IJ + SP 14 0.37460.3559 Delta b IJ 14 3.464 3.197 IJ + SP 14 0.944 1.209 Delta E IJ 144.21 3.91 IJ + SP 14 1.243 1.170

A second figure of merit for the adhesion of these embodiments wasmeasured as a pummel test. Pummel tests are known tests generallyconducted in the auto industry as a measure of glass adhesion tointerlayers. After completion of the pummel testing, embodiments wererated on a scale of 1-10 (in increments of 0.5) based on the observedpercentage of interlayer (film) material remaining. These pummel testsresults are illustrated in FIG. 9 and Table 2 below.

TABLE 2 Variable Print Method N Mean StDev Pummel IJ 3 0.000 0.000Pummel IJ + SP 4 5.000 1.225 Pummel SP 7 8.857 2.393

With reference to FIGS. 9-11 and Tables 1-2, screenprinted partsperformed well but a notable difference can be observed between theinkjet and inkjet with screenprint backer. These differences arestatistically significant as demonstrated by the 95% interval plot forthe mean also shown in FIG. 10. FIG. 11 provides an individual valueplot showing the individual measurements for each embodiment for ease ofreference.

Embodiments described herein can thus combine attributes of differentprinting and decorating processes. For example, inkjet printing can beutilized for customized high-resolution images, followed by screenprinting for its UV stability, durability, and increased white gamut.Such inkjet printing processes can be valued for their high resolution,wide color gamut, ease of customization, low setup time, photo-realisticimages and low cost. Screen printing processes can be valued for theiropacity, durability, solid colors, mass production, and UV stability.Through the combination of multiple technologies, materials andprocesses, an exemplary consumer product can be provided that is notonly attractive in its appearance, but offers safety and userfriendliness in a feature rich product that is cost effective andtime-efficient.

In some aspects of the present disclosure, chemically strengthened glass(e.g., Gorilla Glass) can be used for its strength, scratch and breakresistance as well as its thinness and superior optical clarity. In someembodiments, the thinness of the Gorilla Glass can remove parallaxproblems seen in conventional acrylics and thick soda lime glasses. Thelightweight of Gorilla Glass can also enable easy mounting (e.g., using3M command tape or Velcro tape). Exemplary organophosphate primers canbe employed to provide superior adhesion with long shelf life afterapplication. In some embodiments, the use of a white anti-splinter filmcan eliminate the need for printing white ink and can thus doubleprinting speed and can increase color scheme flexibility, ambiance,contrast and programmability. Embodiments having an edge coating canalso improve drop survivability.

In some embodiments, a method for printing ink on a glass substrate isprovided. The method includes coating a glass substrate with a silanematerial, depositing a first layer of ink on the coated glass substrate,depositing a second layer of ink over the first layer of ink, anddepositing a powder coating onto the second layer of ink. In anotherembodiment, the method includes curing the glass substrate having adeposited powder coating thereon. An exemplary silane material can be,but is not limited to, silanes having no functional groups, silaneshaving one or more functional groups, and combinations thereof. Anexemplary powder coating includes material having inorganic particles,organic particles, thermally activated materials, components whichabsorb ultraviolet radiation, and combinations thereof. The first layerof ink can include a color image having a plurality of colors, and thesecond layer of ink can be solid white. In some embodiments, the glasssubstrate can have a thickness ranging from 0.1 mm to 2.2 mm. In otherembodiments, the glass substrate can be chemically strengthened glass.

In other embodiments a method for printing ink on a glass substrate caninclude the steps of depositing a first powder coating on a glasssubstrate, depositing a first layer of ink on the coated glasssubstrate, depositing a second layer of ink over the first layer of ink,and depositing a second powder coating onto the second layer of ink. Inanother embodiment, the method includes curing the glass substratehaving a deposited second powder coating thereon. The first and secondpowder coatings can include material such as, but not limited to,inorganic particles, organic particles, thermally activated materials,components which absorb ultraviolet radiation, and combinations thereof.Of course, the first and second powder coatings can be different. Thefirst layer of ink can include a color image having a plurality ofcolors, and the second layer of ink can be solid white. In someembodiments, the glass substrate can have a thickness ranging from 0.1mm to 2.2 mm. In other embodiments, the glass substrate can bechemically strengthened glass.

In further embodiments, a method for printing ink on a substrate caninclude the steps of coating a glass substrate with an adhesionpromoter, depositing a first layer of ink on the coated substrate,depositing a second layer of ink over the first layer of ink, anddepositing a powder coating onto the second layer of ink. In anotherembodiment, the method includes curing the glass substrate having adeposited powder coating thereon. Exemplary adhesion promoters caninclude a silane material or a powder coating. An exemplary powdercoating material can include, but is not limited to, inorganicparticles, organic particles, thermally activated materials, componentswhich absorb ultraviolet radiation, and combinations thereof. The firstlayer of ink can include a color image having a plurality of colors, andthe second layer of ink can be solid white. In some embodiments, thesubstrate can be a glass substrate and can have a thickness ranging from0.1 mm to 2.2 mm. This glass substrate can be, in some embodiments,chemically strengthened glass.

In some embodiments a method for printing ink on a substrate isprovided. The method can include pretreating a glass substrate,depositing one or more layers of ink on the pretreated glass substrate,overprinting the deposited one or more layers of ink with an overcoat,and curing the overprinted glass substrate to encapsulate the depositedone or more layers of ink. In some embodiments, the step of pretreatingcan further comprise one or both of cleaning the glass substrate ofcontaminants and coating the glass substrate with an adhesion promoter.An exemplary adhesion promoter can be a silane material, a powdercoating, or an organophosphate material. In another embodiment, the stepof depositing one or more layers of ink can further comprise depositinga layer of white ink. In yet a further embodiment, the step ofdepositing can further comprise inkjetting one or more layers of ink. Anexemplary substrate can be a chemically strengthened glass substratewith a thickness ranging from 0.1 mm to 2.2 mm and/or can be planar orthree dimensional in form. In another embodiment, the method can includedepositing a powder coating on the overprinted substrate before curingthe overprinted glass substrate. Exemplary powder coatings includematerial selected from the group consisting of inorganic particles,organic particles, thermally activated materials, components whichabsorb ultraviolet radiation, and combinations thereof.

In a further embodiment, a method for printing ink on a substrate isprovided. The method includes pretreating a substrate with anorganophosphate primer suspended in a solvent, depositing one or morelayers of ink on a first surface of the pretreated substrate, andlaminating a film onto to the first surface to form an imaged laminate.An exemplary film can be an anti-splinter film and can be white orcolored. Additional films can include, but are not limited to, vinyl,polypropylene, high density polyethylene (HDPE), polyvinyl chloride(PVC), clear or cloudy polyethylene terephthalate (PET), metallizedpolyester, lenticular plastic and/or polymer dispersed liquid crystals(PDLC) films. In some embodiments, the method includes coating portionsor all of the imaged laminate with a polymeric material. This coatedportion(s) can then be cured. Exemplary, non-limiting substrates can bechemically strengthened glass, non-chemically strengthened glass, metal,canvas, wood, or acrylic substrates. In one embodiment, the substratecan be a chemically strengthened glass substrate with a thicknessranging from 0.1 mm to 2.2 mm. In another embodiment, the step ofpretreating a substrate can further comprise soaking or dipping thesubstrate in the organophosphate primer, removing the primer, and dryingthe primed substrate.

While this description may include many specifics, these should not beconstrued as limitations on the scope thereof, but rather asdescriptions of features that may be specific to particular embodiments.Certain features that have been heretofore described in the context ofseparate embodiments may also be implemented in combination in a singleembodiment. Conversely, various features that are described in thecontext of a single embodiment may also be implemented in multipleembodiments separately or in any suitable subcombination. Moreover,although features may be described above as acting in certaincombinations and may even be initially claimed as such, one or morefeatures from a claimed combination may in some cases be excised fromthe combination, and the claimed combination may be directed to asubcombination or variation of a subcombination.

Similarly, while operations are depicted in the drawings or figures in aparticular order, this should not be understood as requiring that suchoperations be performed in the particular order shown or in sequentialorder, or that all illustrated operations be performed, to achievedesirable results. In certain circumstances, multitasking and parallelprocessing may be advantageous.

Ranges can be expressed herein as from “about” one particular value,and/or to “about” another particular value. When such a range isexpressed, examples include from the one particular value and/or to theother particular value. Similarly, when values are expressed asapproximations, by use of the antecedent “about,” it will be understoodthat the particular value forms another aspect. It will be furtherunderstood that the endpoints of each of the ranges are significant bothin relation to the other endpoint, and independently of the otherendpoint.

It is also noted that recitations herein refer to a component of thepresent disclosure being “configured” or “adapted to” function in aparticular way. In this respect, such a component is “configured” or“adapted to” embody a particular property, or function in a particularmanner, where such recitations are structural recitations as opposed torecitations of intended use. More specifically, the references herein tothe manner in which a component is “configured” or “adapted to” denotesan existing physical condition of the component and, as such, is to betaken as a definite recitation of the structural characteristics of thecomponent.

As shown by the various configurations and embodiments illustrated inthe figures, various methods for ink jet printing on glass substrateshave been described.

While preferred embodiments of the present disclosure have beendescribed, it is to be understood that the embodiments described areillustrative only and that the scope of the invention is to be definedsolely by the appended claims when accorded a full range of equivalence,many variations and modifications naturally occurring to those of skillin the art from a perusal hereof.

We claim:
 1. A method for printing ink on a substrate comprising thesteps of: pretreating a glass substrate; depositing one or more layersof ink on the pretreated glass substrate; overprinting the deposited oneor more layers of ink with an overcoat; and curing the overprinted glasssubstrate to encapsulate the deposited one or more layers of ink.
 2. Themethod of claim 1 wherein the step of pretreating further comprises oneor both of cleaning the glass substrate of contaminants and coating theglass substrate with an adhesion promoter.
 3. The method of claim 2wherein the adhesion promoter is a silane material, a powder coating, oran organophosphate material.
 4. The method of claim 1 wherein the stepof depositing one or more layers of ink further comprises depositing alayer of white ink or inkjetting one or more layers of ink.
 5. Themethod of claim 1 wherein the substrate is a glass substrate with athickness ranging from 0.1 mm to 2.2 mm.
 6. The method of claim 1wherein the substrate is planar or three dimensional.
 7. The method ofclaim 5, wherein the glass substrate is chemically strengthened.
 8. Aproduct made from the process of claim
 1. 9. The method of claim 1further comprising the step of depositing a powder coating on theoverprinted substrate before curing the overprinted glass substrate,wherein the powder coating includes material selected from the groupconsisting of inorganic particles, organic particles, thermallyactivated materials, components which absorb ultraviolet radiation, andcombinations thereof.
 10. A method for printing ink on a substratecomprising the steps of: pretreating a substrate with an organophosphateprimer suspended in a solvent; depositing one or more layers of ink on afirst surface of the pretreated substrate; and laminating a film onto tothe first surface to form an imaged laminate.
 11. The method of claim10, wherein the film comprises an anti-splinter film and is white orcolored.
 12. The method of claim 10, wherein the film is selected fromthe group consisting of vinyl, polypropylene, high density polyethylene(HDPE), polyvinyl chloride (PVC), clear or cloudy polyethyleneterephthalate (PET), metallized polyester, lenticular plastic andpolymer dispersed liquid crystals (PDLC).
 13. The method of claim 10further comprising the step of coating portions or all of the imagedlaminate with a polymeric material and optionally curing the coatedportions of the imaged laminate.
 14. The method of claim 10 wherein thesubstrate is a chemically strengthened glass, non-chemicallystrengthened glass, metal, canvas, wood, or acrylic substrate.
 15. Themethod of claim 10 wherein the step of pretreating a substrate furthercomprises soaking or dipping the substrate in the organophosphateprimer, removing the primer, and drying the primed substrate.
 16. Alaminate comprising: a substrate pretreated with an organophosphateprimer suspended in a solvent; one or more layers of ink deposited on afirst surface of the pretreated substrate; and a film laminated on theone or more layers to form an imaged laminate.
 17. The laminate of claim16, wherein the film comprises an anti-splinter film and is white orcolored.
 18. The laminate of claim 16, wherein the film is selected fromthe group consisting of vinyl, polypropylene, high density polyethylene(HDPE), polyvinyl chloride (PVC), clear or cloudy polyethyleneterephthalate (PET), metallized polyester, lenticular plastic andpolymer dispersed liquid crystals (PDLC).
 19. The laminate of claim 16,further comprising a polymeric material coating portions or all of theimaged laminate.
 20. The laminate of claim 16, wherein theorganophosphate primer is selected from the group consisting of amethacrylated phosphoric acid, monoalkyl phosphate, dialkyl phosphate,di-n-butylphosphate, vinyl phosphonic acid, vinyl phosphonic acid methylester, phosphates of hydroxy alkyl acrylates or methacrylates like thephosphate of 2-hydroxyethyl acrylate, or the phosphate of 2-hydroxyethylmethacrylate, 10-methacryloyloxydecyl dihydrogen phosphate,10-acryloyloxydecyl dihydrogen phosphate, bis(2-acryloyloxyalkyl)acidphosphate, bis(2-methacryloyloxyalkyl)acid phosphate, and the phosphateof caprolactone modified hydroxyalkyl acrylate or methacrylate,N-(dimethylphosphonomethyl)acrylamide, phosphonic acid,P-[[(1-oxo-2-propen-1-yl)amino]methyl]-, vinyl-,bis(2-chloroethyl)phosphonic acid ester,tris(2-chloroisopropyl)phosphate, tris(2-chloroethyl)phosphate,tris(1,3-dichloroisopropyl)phosphate, other monomeric and oligomericchloroalkyl phosphate esters, and phosphonic acids, andP-[[bis(2-hydroxyethyl)amino]methyl]-, and diethyl ester.